CN1772937A - Super magnetostrictive material with super wide work temperature range - Google Patents

Super magnetostrictive material with super wide work temperature range Download PDF

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CN1772937A
CN1772937A CN 200510086883 CN200510086883A CN1772937A CN 1772937 A CN1772937 A CN 1772937A CN 200510086883 CN200510086883 CN 200510086883 CN 200510086883 A CN200510086883 A CN 200510086883A CN 1772937 A CN1772937 A CN 1772937A
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magnetostriction
temperature range
super
rare earth
temperature
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CN100372958C (en
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张深根
曲选辉
秦明礼
左志军
何新波
段柏华
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University of Science and Technology Beijing USTB
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Abstract

The present invention provide one kind of super magetostrictive material with super wide work temperature range, and belongs to the field of super magetostrictive RE material. The super magetostrictive material is intermetallic compound alloy comprising CsCl type Tb1-xDyxZn phase and MgCu2 type Tb1-yDyy(Fe1-zTz)2 phase, where x=0.00-1.00, y=0.60-0.90, z=0.00-0.40, and T is 1-6 elements of Ni, Co, Cr, V, Mn and Al. The present invention has the advantages of the magetostrictive coefficient of 0.05-0.50 % in the temperature range of 77-523 K and thus the work temperature range of 77-523 K.

Description

A kind of rare earth ultra-magnetostriction material that can use at super wide temperature range
Technical field
The invention belongs to the rare earth ultra-magnetostriction material technical field, a kind of rare earth ultra-magnetostriction material that can use at super wide temperature range particularly is provided.
Background technology
People such as U.S. A.E.Clark study TbFe 2, DyFe 2And SmFe 2Deng the magnetostriction performance of rare earth intermetallic compound, and with the TbFe of magnetocrystalline anisotropy field opposite in sign 2And DyFe 2Form (Tb, Dy) Fe 2, making it becomes practical rare earth ultra-magnetostriction material, and has applied for U.S. Pat 3,949,351 on April 6th, 1976.Because above-mentioned rare earth ultra-magnetostriction material can be realized the energy transformation between magnetic () energy-machinery (sound) energy fast, can be widely used in industries such as navigation, aviation, machinery, oil, therefore, this material becomes one of research focus rapidly.The patent of relevant this rare earth ultra-magnetostriction material is many, but concentrates on MgCu mostly 2The REFe of type structure 2Compound and alloying constituent thereof, manufacturing process aspect between big metalloid.For example early stage patent mainly concentrates on the theory and the composition Study of rare earth ultra-magnetostriction material.The US4 of application on December 29th, 1981,308,474 main description chemical formulas are Tb xDy 1-xFe 2-w, Tb xHo 1-xFe 2-w, Sm xDy 1-xFe 2-w, Sm xHo 1-xFe 2-w, Tb xHo yDy zFe 2-wOr Sm xHo yDy zFe 2-w(0≤W≤0.20, x+y+z=1) polycrystalline orientation or monocrystalline magnetostriction materials belong to MgCu 2The REFe of type structure 2Compound and alloying constituent patent thereof between big metalloid.The US4 of application on May 29 nineteen eighty-three, 378,258, mainly describing chemical formula is R xT 2-x(R is rare earth or mishmetal, and T is one or more of Fe, Ni, Co, Mn, and 0＜x＜1=has set forth magnesium-yttrium-transition metal and substituted Fe, belongs to MgCu 2Type structural intermetallic compounds and alloying constituent patent thereof.The US4 of application on September 2nd, 1986,609,402 have announced that the vertical area process of smelting prepares rare earth ultra-magnetostriction material.The technology that this patent is set forth is that first melting obtains Tb-Dy-Fe prealloy rod, fixes by upper and lower anchor clamps then, adopts high frequency (about 450kHz) ruhmkorff coil to distinguish molten the processing from the bottom to top and obtains the rareearth super magnetostrictive bar.September in 1988 U.S. on the 13rd patent US4,770,704 have announced that a kind of down draw process prepares rare earth ultra-magnetostriction material.April in 1989 U.S. on the 4th patent US4,818,304 have announced rareearth super magnetostrictive bar thermomagnetic treatment technology.Above-mentioned two patents have been set forth the Tb-Dy-Fe alloy and have been formed behind the alloy liquation in aperture by the crucible bottom silica tube below flowing into then by induction melting that directional freeze obtains the rareearth super magnetostrictive bar, carry out 400 ℃ of-600 ℃ of thermomagnetic treatment at last.June 20 nineteen ninety Japanese patent laid-open 4-52246 to have set forth chemical formula be RFe x(R is a rare earth metal, and x=1.7-2.0) alloy adopts the powder process of fast quenching thin strap technology, and pressure is to carry out hot pressing or hot isostatic pressing shaping more than 0.8 ton/square centimeter, obtains the technology of sintering rare-earth ultra-magnetic telescopic then 350 ℃ of-700 ℃ of thermal treatments.May in 1992 U.S. on the 19th patent US5,114,467 have announced that a kind of using plasma melting technology prepares rare earth ultra-magnetostriction material.This process using screw thread feed appliance is sent previously prepared master alloy powder into the plasma melting district and is formed the alloy liquation, the alloy liquation flows in the water-cooled mould of bottom, and mould moves downward with certain speed and carries out directional freeze and obtain rare earth ultra-magnetostriction material.It is (Tb that the Chinese patent 93106941.6 of application on June 15th, 1993 discloses chemical formula 1-x-yDy xR y) (Fe 1-z-pTi zM p) Q(x=0.65-0.80 wherein, y=0.001-0.1, z=0.00-0.1, p=0.00-0.1, Q=1.75-2.55, R are Ho, Er, Sm, Pr etc., M is V, Cr, Co, Si, Zr etc.) production technique.On February 27th, 1997 Japanese patent laid-open 10-242,543 to have set forth chemical formula be Tb 1-xDy xFe 2(0.5＜x＜0.75) agglutinate rare earth ultra-magnetostriction material preparation technology.The Chinese patent 98101191.8 of on April 14th, 1998 application disclose＜and 110〉axial orientation be the rare earth ultra-magnetostriction material preparation technology who leads.The Chinese patent 01203029.5 of application on January 16 calendar year 2001 discloses the device of scale continuous production rare earth ultra-magnetostriction material and the Chinese patent 03156926.9 of application on September 15th, 2003 discloses rare earth ultra-magnetostriction material one-step method production process and products thereof.It is rare earth ultra-magnetostriction material and preparation method thereof that the Chinese patent 200510039001.8 of application on April 21st, 2005 discloses a kind of Pr.
Above-mentioned patent is related is MgCu 2The REFe of type structure 2Compound and alloying constituent and manufacturing process between big metalloid do not relate to the working temperature of material, belong to the material of use normal temperature under.Along with the magnetostriction materials Application Areas constantly enlarges (as space flight), require its practical temperature to have high temperature performance concurrently, press for the super wide temperature range of exploitation and use novel rareearth super magnetostrictive material to satisfy space flight and rocket launching demand.It is Tb that the Chinese patent 02121447.6 of application on June 21st, 2002 discloses chemical formula 0.3-0.5Dy 0.5-0.7(Fe, Co, Al, Mn) 1.90-1.96, obtain at-80 ℃～120 ℃ temperature range available rare earth ultra-magnetostriction materials by the ratio of adjusting Tb and Dy and the spin reorientation temperature of adding change alloys such as alloying element Co, A1, Mn.It is Tb that the Chinese patent 03154426.6 of application on September 28th, 2003 discloses chemical formula xDy 1-x(Fe 1-yT y) zWherein x=0.01-0.43, y=0-0.30, z=1.50-2.00, T is Cr, V, four kinds of elements of Co, Ni, by reducing the spin reorientation temperature and improving the use temperature that Curie temperature is widened material, obtain-80 ℃～150 ℃ temperature range available rare earth ultra-magnetostriction materials.These two patents have been widened the use temperature of traditional rare earth giant magnetostrictive material greatly.But the material that above-mentioned two patents are invented is difficult to meet the demands in space field and rocket launching.Because the space environment cold condition is following and the rocket liquid fuel temperature is lower than-80 ℃, and temperature is higher than 150 ℃ under the space environment hot conditions, even reaches 250 ℃.
Summary of the invention
The object of the present invention is to provide a kind of rare earth ultra-magnetostriction material that can use at super wide temperature range, can in the 77K-523K temperature range, use novel rareearth super magnetostrictive material, overcome the shortcoming of traditional magnetostriction materials use temperature narrow range.
The present invention is by the Tb with CsCl type structure 1-xDy xZn and have a MgCu 2Type structure Tb 1-yDy y(Fe 1-zT z) 2The alloy that the two-phase intermetallic compound is formed, x=0.00-1.00 wherein, y=0.60-0.90, z=0.00-0.40, T are 1～6 kind of element of Ni, Co, Cr, V, Mn, Al element.
Tb with CsCl type structure 1-xDy xThe feature of Zn is: have the big magnetostriction coefficient λ of uniaxial orientation,＜100〉direction coefficient of dilatation λ at low temperature 100Greater than＜111〉the coefficient of dilatation λ of direction 111, i.e. λ 100＞λ 111As shown in Figure 1, along with x is different with temperature, Tb 1-xDy xThe EMD of Zn changes, and EMD is＜100 in the time of can obtaining low temperature by adjusting x〉the material of uniaxial orientation; Have comparatively ideal Young's modulus and ultimate compression strength, be particularly suitable for using in the 77K-273K temperature range.
Has MgCu 2The Tb of type structure 1-yDy y(Fe 1-zT z) 2Different directions magnetostriction coefficient difference, and λ 111＞＞λ 100Be lower than the spin reorientation temperature T rThe time EMD be＜100, λ descends along with temperature reduces sharply, is higher than T rThe time EMD be＜111, the rising of λ temperature slowly descends.Therefore, Tb 1-yDy y(Fe 1-zT z) 2At T rThere is the magnetostriction coefficient of a maximum in (between 200K～300K).As shown in Figure 2, chemical formula is Tb 0.27Dy 0.73Fe 2Maximum magnetostriction coefficient about-10 ℃, when temperature was lower than-10 ℃, magnetostriction coefficient sharply descended, and almost can't use.
Rare earth ultra-magnetostriction material of the present invention is by the Tb with CsCl type structure 1-xDy xZn and have a MgCu 2Type structure Tb 1-yDy y(Fe 1-zT z) 2The alloy that the two-phase intermetallic compound is formed has made full use of Tb when low temperature 1-xDy xThe Zn performance makes full use of Tb when high temperature 1-yDy y(Fe 1-zT z) 2Performance, thus obtain to have the type material of 0.05%～0.50% magnetostriction coefficient in the 77K-523K temperature range.Table 1 is the performance of novel rareearth super magnetostrictive material of the present invention.
Table 1 novel rareearth super magnetostrictive material is at the magnetostriction coefficient of differing temps scope
Material Temperature range (K) Magnetostriction coefficient (%)
Tb 1-xDy xZn、Tb 1-yDy y(Fe 1-zT z) 2 77-253 0.50-0.20
The symbol compound system 253-523 0.20-0.05
The present invention prepares above-mentioned materials directional solidification processes, powder metallurgical sintering process and powder metallurgy bonding process etc.
The invention has the advantages that: magnetostriction materials have 0.05%～0.50% magnetostriction coefficient in the 77K-523K temperature range, can use in the 77K-523K temperature range.
Description of drawings
Fig. 1 is Tb of the present invention 1-xDy xThe phasor of Zn easy magnetization axis EMD and x and temperature.
Fig. 2 is Tb of the present invention 027Dy 0.73Fe 2The relation of coefficient of dilatation λ and temperature under different pressures.
Embodiment
(1) directional solidification processes
With purity 99.5% Tb, Dy, Fe, Zn proportioning Tb 0.3Dy 0.7Zn and Tb 0.28Dy 0.72Fe 2, adopt the high vacuum apparatus for directional solidification to carry out directed vacuum melting, directional freeze and thermal treatment and obtain having CsCl type structure and have MgCu 2The alloy of type structure two phase composites.The concrete operations step is as follows:
The first step: shove charge and vacuumizing.Accurately the various alloying elements of proportioning are built bell in the apparatus for directional solidification smelting pot of packing into, start mechanical pump and vacuumize when reaching 5Pa, and the startup diffusion pump vacuumizes and reaches 10 -2Behind the Pa, close argon gas that vacuum valve charges into about 0.10atm and carry out in the cleaning oven 3 times.When vacuum tightness reaches 10 -3Behind the Pa, close vacuum valve, in stove, charge into the 0.5atm argon gas.
Second step: directional freeze.Start power supply and carry out heating raw and fusing formation molten alloy to smelting pot; Simultaneously the directional freeze insulated tank is heated to 1450 ℃.Molten alloy is poured in the insulated tank, starts servomotor and all pull out insulated tank with the 120mm/h velocity pull-down up to the rareearth super magnetostrictive bar by lifting leading screw.Guarantee that in downdraw process heat is by drop-down direction heat radiation.
The 3rd step: thermal treatment.The temperature that reduces insulated tank starts servomotor and heat-treats 6h by lifting leading screw lifting rareearth super magnetostrictive bar up to all entering insulated tank to 900 ℃ of thermal treatment temps, obtains required novel rareearth super magnetostrictive bar at last.The performance of material is as shown in table 2.
The material of table 2 directional solidification processes preparation is at the magnetostriction coefficient of differing temps scope
Material Temperature range (K) Magnetostriction coefficient (%)
Tb 0.3Dy 0.7Zn、Tb 0.28Dy 0.72Fe 2 77-253 0.45-0.20
The symbol compound system 253-523 0.18-0.11
(2) powder metallurgical sintering process
With purity 99.5% Tb, Dy, Fe, Zn proportioning Tb 0.3Dy 0.7Zn and Tb 0.28Dy 0.72(Fe 0.90Ni 0.01Co 0.01Cr 0.02V 0.02Mn 0.03Al 0.01) 2, adopt high vacuum melting equipment to prepare mother alloy, adopt media protection ball milling or technology powder process such as airflow milling or vacuum quick quenching, adopt magnetic field compression moulding then, carry out sintering and thermal treatment at last and obtain having CsCl type structure and have MgCu 2Type structure biphase sintering novel rareearth super magnetostrictive material.The concrete operations step is as follows:
The first step: mother alloy preparation.Accurately the various alloying elements of proportioning are built bell in the vacuum melting equipment smelting pot of packing into, start mechanical pump and vacuumize when reaching 5Pa, and the startup diffusion pump vacuumizes and reaches 10 -2Behind the Pa, close argon gas that vacuum valve charges into about 0.10atm and carry out in the cleaning oven 3 times.When vacuum tightness reaches 10 -3Behind the Pa, close vacuum valve, in stove, charge into the 0.50atm argon gas.Start power supply and carry out heating raw and fusing formation molten alloy to smelting pot; The molten alloy junker mold of casting is obtained having CsCl type structure and has a MgCu 2The mother alloy of type structure two phase composites.
Second step: powder process.Adopt media protection ball milling or technology powder process such as airflow milling or vacuum quick quenching, powder size is at-200 orders.The oxygen level that will control powder during powder process is low as far as possible.
The 3rd step: magnetic field compression moulding.Powder is orientated compacting at the pressing under magnetic field machine, obtains to have＜100〉orientation Tb 1-xDy xZn and＜112〉(or＜110 or＜113) orientation Tb 1-yDy y(Fe 1-zT z) 2Pressed compact.
The 4th step: sintering.Pressed compact carries out vacuum or protection of inert gas sintering, and sintering temperature is 1050 ℃-1200 ℃, and sintering time is 2h.
The 5th step: thermal treatment.Sintered compact carries out 950 ℃ of thermal treatment 8h.The performance of material is as shown in table 3.
The material of table 3 powder metallurgical sintering process preparation is at the magnetostriction coefficient of differing temps scope
Material Temperature range (K) Magnetostriction coefficient (%)
Tb 0.3Dy 0.7Zn and 77-253 0.30-0.12
Tb 0.28Dy 0.72(Fe 0.90Ni 0.01Co 0.01Cr 0.02V 0.02Mn 0.03Al 0.01) 2The symbol compound system 253-523 0.12-0.10
(3) powder metallurgy bonding process
With purity 99.5% Tb, Dy, Fe, Zn proportioning Tb 0.28Dy 0.72Zn and Tb 0.40Dy 0.60(Fe 0.60Ni 0.10Co 0.10Cr 0.10Mn 0.10) 2, adopting high vacuum melting equipment to prepare mother alloy, adopt media protection ball milling or technology powder process such as airflow milling or vacuum quick quenching, binding agent and coupling agent and powder is mixing, and binding agent can be thermosetting resin or thermoplastic resin.Adopt magnetic field compression moulding then, be cured at last and obtain having CsCl type structure and have a MgCu 2Type structure biphase bonding novel rareearth super magnetostrictive material.The concrete operations step is as follows:
The preparation of the first step mother alloy, the second step powder process and powder metallurgical sintering process are similar.
The 3rd step: mixing.Binding agent and coupling agent and powder are mixing, and binding agent can be thermosetting resin or thermoplastic resin.The binding agent consumption is 2.00%, coupling agent consumption 0.20%.
The 4th step: magnetic field compression moulding.Powder is orientated compacting at the pressing under magnetic field machine, obtains to have＜100〉orientation Tb 1-xDy xZn and＜112〉(or＜110 or＜113) orientation Tb 1-yDy y(Fe 1-zT z) 2Pressed compact.
The 4th step: solidify.Pressed compact carries out vacuum or rare gas element or air set.Solidification value is 150 ℃, and be 2h set time.The performance of material is as shown in table 4.
The material of table 4 powder metallurgy bonding process preparation is at the magnetostriction coefficient of differing temps scope
Material Temperature range (K) Magnetostriction coefficient (%)
Tb 0.28Dy 0.72Zn and 77-253 0.25-0.10
Tb 0.40Dy 0.60(Fe 0.60Ni 0.10Co 0.10Cr 0.10Mn 0.10) 2The symbol compound system 253-523 0.10-0.05

Claims (2)

1. a novel super wide temperature is used rare earth ultra-magnetostriction material, it is characterized in that it being Tb by having CsCl type structure 1-xDy xZn and have a MgCu 2Type structure Tb 1-yDy y(Fe 1-zT z) 2The alloy that the two-phase intermetallic compound is formed, x=0.00-1.00 wherein, y=0.60-0.90, z=0.00-0.40, T are 1～6 kind of element of Ni, Co, Cr, V, Mn, Al.
2. use rare earth ultra-magnetostriction material according to the described novel super wide temperature of claim 1, it is characterized in that: these magnetostriction materials have 0.05%～0.50% magnetostriction coefficient in the 77K-523K temperature range, use in the 77K-523K temperature range.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102766792A (en) * 2012-06-18 2012-11-07 河北工业大学 Preparation method of binding rare-earth iron giant magnetostrictive material
CN102950103A (en) * 2011-08-23 2013-03-06 北京斯克维思仪表有限公司 Ceramic transducer and ceramic transduction type magnetostriction transmitter
CN106098929A (en) * 2016-07-24 2016-11-09 泉州海岸线新材料科技有限公司 The formula of a kind of high-performance bonding rare earth magnetostriction materials and preparation technology
CN115058771A (en) * 2022-06-22 2022-09-16 清华大学 Preparation method and device of rare earth-iron-based magnetostrictive single crystal material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10242543A (en) * 1997-02-27 1998-09-11 Seiko Epson Corp Resin bonding type magnetostrictive material
US6451131B1 (en) * 2001-06-29 2002-09-17 Energen, Inc. Terbium-dysprosium-iron magnetostrictive materials and devices using these materials
CN1466231A (en) * 2002-06-21 2004-01-07 北京航空航天大学 Rareearth super magnetostrictive material with wide temp. range
CN100356603C (en) * 2002-07-04 2007-12-19 北京磁伸稀土技术发展有限公司 Novel rareearth super magnetostrictive material and preparation method thereof
CN1322599C (en) * 2003-09-28 2007-06-20 北京航空航天大学 Novel wide temperature domain giant magnetostriction material and its preparing method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102950103A (en) * 2011-08-23 2013-03-06 北京斯克维思仪表有限公司 Ceramic transducer and ceramic transduction type magnetostriction transmitter
CN102950103B (en) * 2011-08-23 2015-08-19 北京斯克维思仪表有限公司 Ceramic transducer and ceramic transduction type magnetostriction transmitter
CN102766792A (en) * 2012-06-18 2012-11-07 河北工业大学 Preparation method of binding rare-earth iron giant magnetostrictive material
CN102766792B (en) * 2012-06-18 2013-12-25 河北工业大学 Preparation method of binding rare-earth iron giant magnetostrictive material
CN106098929A (en) * 2016-07-24 2016-11-09 泉州海岸线新材料科技有限公司 The formula of a kind of high-performance bonding rare earth magnetostriction materials and preparation technology
CN115058771A (en) * 2022-06-22 2022-09-16 清华大学 Preparation method and device of rare earth-iron-based magnetostrictive single crystal material

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